EP1251745B1 - A process for hard panning of chewable cores and cores produced by the process - Google Patents

A process for hard panning of chewable cores and cores produced by the process Download PDF

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Publication number
EP1251745B1
EP1251745B1 EP01903845A EP01903845A EP1251745B1 EP 1251745 B1 EP1251745 B1 EP 1251745B1 EP 01903845 A EP01903845 A EP 01903845A EP 01903845 A EP01903845 A EP 01903845A EP 1251745 B1 EP1251745 B1 EP 1251745B1
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EP
European Patent Office
Prior art keywords
coating
drying
air
process according
cores
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP01903845A
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German (de)
English (en)
French (fr)
Other versions
EP1251745A1 (en
Inventor
Juha Nurmi
Tammy Pepper
Juha Oravainen
Mike Bond
Ian Fairs
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Danisco Sweeteners Oy
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Danisco Sweeteners Oy
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Application filed by Danisco Sweeteners Oy filed Critical Danisco Sweeteners Oy
Priority to DK01903845T priority Critical patent/DK1251745T3/da
Publication of EP1251745A1 publication Critical patent/EP1251745A1/en
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Classifications

    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23GCOCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G4/00Chewing gum
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23GCOCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G4/00Chewing gum
    • A23G4/06Chewing gum characterised by the composition containing organic or inorganic compounds
    • A23G4/10Chewing gum characterised by the composition containing organic or inorganic compounds characterised by the carbohydrates used, e.g. polysaccharides
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23GCOCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G3/00Sweetmeats; Confectionery; Marzipan; Coated or filled products
    • A23G3/02Apparatus specially adapted for manufacture or treatment of sweetmeats or confectionery; Accessories therefor
    • A23G3/20Apparatus for coating or filling sweetmeats or confectionery
    • A23G3/2092Apparatus for coating with atomised liquid, droplet bed, liquid spray
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23GCOCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G4/00Chewing gum
    • A23G4/02Apparatus specially adapted for manufacture or treatment of chewing gum
    • A23G4/025Apparatus specially adapted for manufacture or treatment of chewing gum for coating or surface-finishing
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23GCOCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G4/00Chewing gum
    • A23G4/18Chewing gum characterised by shape, structure or physical form, e.g. aerated products
    • A23G4/20Composite products, e.g. centre-filled, multi-layer, laminated

Definitions

  • the present invention relates to a process for the hard panning of chewable cores in a rotary pan wherein a syrup containing crystallizable sugar(s) and/or polyol(s) such as xylitol is intermittently sprayed over a bed of the cores and the cores are dried between sprayings with a flow of air.
  • the invention relates especially to the improved control of the panning process which enables a faster panning and thereby a considerable saving in the time required for providing cores with hard coatings.
  • the invention also relates to cores panned by a process according to the invention and especially to chewing gums coated with a hard coating of xylitol.
  • the panning technology has provided long drying times to allow the crystallization to proceed properly in the layer.
  • long drying times increase the cost of panning.
  • compounds such as xylitol and sorbitol the solubility and viscosity of the compound require low temperature panning (see "Coating with sorbitol. A Comparison of properties of sorbitol-mannitol other polyols and sugars" by Francis Devos, Roquette Freres, Manufacturing Confectioner. November 1980).
  • Xylitol is rather broadly used in non-cariogenic chewing gums, confectionery and pharmaceuticals.
  • a fairly low temperature such as 20 to 25°C is used and care is taken to dry the cores properly between sprayings. This provides a good and hard coating but requires long process times. If the panning procedures could be speeded up, the capacity of the equipment could be increased and cost savings could be obtained.
  • polyols such as xylitol
  • the present invention seeks to provide improvements in panning procedures to alleviate the problems discussed above and to provide a product with equal or improved quality and shelf-life.
  • the present invention has been worked out primarily with xylitol but in its broadest sense it is applicable also to panning with other polyols and for the control of panning with sugars.
  • the present invention relates to a process for the production of chewable coated cores by hard panning of chewable cores in a coating pan or drum wherein a syrup containing crystallizable polyol(s) and/or sugar(s) is intermittently sprayed over a rotating bed of the cores and the cores are dried between sprayings with a flow of air.
  • the invention is characterized in that the drying of the cores between sprayings is controlled by controlling parameters of the drying air in such a way as to intentionally leave a substantial residual moisture in the drying coating layer at the start of a subsequent spraying phase.
  • substantially residual moisture as used throughout this specification and claims is intended to mean a moisture which is substantially higher than the moisture left in the coating layer in conventional panning procedures.
  • conventional panning it is considered necessary to dry the sprayed coating layer to a fully dry condition before the next layer is sprayed. It is also considered necessary to perform the drying slowly so that the crystallization and drying are in balance. A moist and/or improperly crystallized layer is considered to provide a very poor product.
  • a normal coating is performed slowly and does not stop until the drying is substantially complete to avoid having sticky cores which adhere to each other.
  • a good panner also knows that the drying should not continue for too long since then the cores will become brittle and will start to produce dust which impairs the surface of the coating.
  • the drying of the cores may also be monitored by measuring the humidity in the bed or in the drum or the humidity of the outlet air. The drying is complete when the humidity does not change anymore and its gradient reaches a plateau.
  • the control is preferably made by monitoring the relative humidity of the outlet air.
  • the drying would be complete by conventional standards when the relative humidity gradient has reached a plateau. This plateau indicates what in the specification and claims is called the "basic level".
  • This basic level is the humidity level that the conventional panning would aim at.
  • the drying is stopped before the humidity reaches its basic level and its gradient flattens out to a plateau.
  • a residual moisture is intentionally left in the cores. This may be seen in that the air is still effectively although slowly removing moisture from the cores and the humidity of the outlet air keeps decreasing.
  • the present invention is based on the realization that it is not necessary to dry the cores completely.
  • the critical maximum level of residual moisture or rather the critical minimum level of dryness that must be reached is the level where the outer surface of the cores is completely dry.
  • the layer underneath it still contains a substantial amount of its moisture. This residual moisture has in the prior art been substantially completely removed and drying has continued until all of the syrup has crystallized or at least solidified. Removing this moisture is slow and hence it slows down the whole process.
  • the drying air parameters are preferably selected from air humidity, air temperature, air flow speed, air flow time and air flow direction. A combination of two or more of the parameters may be required to provide the desired control.
  • the drying is performed with air having a higher temperature than what has been conventionally used and the residual moisture is retained in the core layer by stopping the blowing of drying air to the bed of cores before the relative humidity of the drying air indicates total drying of the coating.
  • control of the drying time is based on the relative humidity of the outlet air from the pan. The spraying starts immediately after the drying air flow has stopped.
  • control may also be performed by adjusting the temperature and/or the humidity and the flow time of the inlet air, or by some other combination of parameters, which is well understood by those skilled in the art.
  • the "substantial" amount of moisture left in the layer will differ with different coating compounds and different conditions.
  • the limit of moisture retained in the layer and the trigger point at which the next spraying should start may be worked out and optimized by tests which are well within the competence of those skilled in the art.
  • the cores or pellets may, for instance, be checked visually and by feel to ascertain that the outer "skin" of the last layer is dry.
  • the preferred method according to the invention is to monitor the outlet air relative humidity.
  • the relative humidity should be at least 1% higher than conventional. Even this small residual moisture may speed up the process considerably since the drying at the end is so slow.
  • the relative humidity at the start up of the next spraying phase is more than 3% and preferably 5-10% higher than the conventional value.
  • the polyols which are useful for panning according to the present invention are crystallizable polyols which are conventionally used for providing a hard coating on cores.
  • the polyols are especially selected from xylitol, sorbitol, maltitol, isomalt, mannitol or mixtures thereof.
  • isomalt is intended to cover both isomalt and its separate crystallizable components.
  • the preferred polyol is xylitol.
  • the sugar useful in the present invention is a crystallizable sugar useful as a hard coating. Usually the sugar would be selected from saccharose, fructose and glucose.
  • the present invention concerns a process for the hard panning of chewable cores in a rotary pan wherein a syrup of a polyol such as xylitol syrup is intermittently sprayed over a bed of the cores and the cores are dried between sprayings with a flow of air.
  • a syrup of a polyol such as xylitol syrup
  • the drying air temperature is generally close to ambient temperatures which makes the coating procedure slow but allows crystallization to proceed properly in the coating layer.
  • the temperature of the bed should be raised but it must not be elevated above the temperature at which the cores in the bed will melt or deteriorate. Another critical limit for the elevated temperature is provided by the melting point of the coating compound.
  • the temperature of the bed of chewable cores is raised to a temperature above 25°C.
  • the temperature of the bed may be raised to 45 °C, preferably between 30 and 40 °C, for at least a part of the total coating procedure.
  • the drying during this part of the procedure is performed with air having a temperature above 25°C.
  • the temperature of the inlet air may be raised to 75°C. preferably to between 30 and 65°C.
  • the present invention provides a chewable core panned by a process as defined above.
  • the core is preferably a chewing gum coated with a hard coating of xylitol.
  • the present invention makes the coating process quicker and more efficient and still produces a product with a comparable or better crunch and shelf-life.
  • a controlled process is provided wherein the conventional drying air temperature (about 20 to 25°C) is raised to a higher temperature.
  • a high temperature in the panning with a polyol such as xylitol was clearly against the judgement of the person skilled in the art.
  • the high temperature panning results in good quality cores while the process time are reduced as much as 40% from the standard procedure.
  • the coating quality was very good.
  • the coating and core crunch was comparable to standard cores and the cores had a good shelf-life.
  • the bed temperature is raised and the drying process is controlled by the relative humidity of the outlet air.
  • the drying times can be significantly shortened with the higher temperature drying, and set times can be obtained from the measured relative humidity values.
  • the first coating cycles are performed at normal temperature (about 20 to 25 °C) to make good start up. Thereafter the temperature is raised and then most of the cycles are performed with hot drying air. and, preferably, the final coating steps are again performed at normal temperature to provide typical post treatment conditions.
  • the high temperature drying period is preferably controlled by monitoring the outlet air humidity.
  • the drying is stopped before the relative humidity of the drying air has reached its basic level.
  • the basic level of the relative humidity (RH) of the outlet air means the RH at its lowest point i.e. the level where the RH gradient has reached a plateau.
  • RH relative humidity
  • the slope of the decreasing RH curve flattens out towards the end of the drying pause. Drying is quick at the start and slow towards the end. In the present invention the conventional end point is not reached.
  • the next spraying is started before the cores have been fully dried out. Although the amount of moisture left is not large, the cutting off of the drying saves a lot of time since the drying is slow at this point. At elevated temperatures the drying is faster due to the elevated bed temperature.
  • the drying is stopped and the next spraying is started when the relative humidity of the outlet air is 1 to 10 percentages higher, preferably 4 to 8 percentages higher than that of the basic level. It is especially preferred to start the next spraying when the RH of the outlet air is more than 3% higher than the basic level. Very good results have been observed with an RH of about 5% higher RH values and an elevated temperature of the drying air. Stopping the drying at this point means that an amount of moisture is intentionally left in the coating. The conventional balance between drying and crystallization is not achieved. By leaving some moisture in the coating the later crystallization of the xylitol is surprisingly improved and the crunch and quality of the product after tempering is improved.
  • the cores may be coated in any conventional coating apparatus.
  • the cores normally rotate in a coating bed.
  • Coating solution is fed in cycles to the coating apparatus.
  • the coating apparatus rotate essentially all the coating time.
  • the target is to get chewing gum having smooth coating layers of a sufficient thickness. Thus, up to 100 or more cycles can be applied. Normally about 50 to 60 cycles are applied for chewing gums.
  • a conventional coating process is made in cycles which include (i) a syrup spraying phase; (ii) a rotating phase without spraying (i.e. a pause); and (iii) an air drying phase. Sometimes, however, the pause is left out.
  • a syrup containing polyol or sugar is sprayed on a rotating bed of cores to be coated. Basically as much as possible syrup is sprayed, but if too much is added the cores tend to adhere to each other.
  • the syrup spreads uniformly on the pellets or cores.
  • the drying air flow is often maintained but the bed is by-passed so that no air flow contacts the bed.
  • the air flow may be maintained or by-passed.
  • the drying air is supplied to the bed.
  • the drying air is normally dried before use by cooling it below its dew point so as to remove moisture. Then the dry air is generally heated to the desired temperature.
  • the core material of most chewing gums or the like heat sensitive material does not tolerate too high drying temperatures. Therefore, it is preferred in the practice of the invention to use in the first cycles drying air with a standard ambient temperature to create "protective" layers on the cores. After the protecting layers are formed the temperature of the drying air is raised and the higher air temperature gradually raises also the bed temperature.
  • the process is controlled by monitoring drying air parameters which control the residual moisture. It is especially preferred to control the outlet air humidity (moisture concentration of the outlet air), the air flow rate or time, and/or the speed or direction of the air.
  • the drying phase is stopped before the drying is completed. When a suitable humidity is reached the drying is interrupted.
  • the differential between the basic RH and the trigger point for syrup application is preferably between 1-10 percentages.
  • the actual value needs to be varied depending on the bed temperature and the inlet air RH. At higher inlet air humidities the difference between basic and trigger point RH should be smaller.
  • the desire is to ascertain that there is residual moisture in the coating.
  • the efficiency of the drying air improves as the RH of the inlet air is lowered and the difference between trigger point RH and basic level can be increased.
  • the relative humidity of the drying air at the outlet is preferably monitored and the drying air is stopped slightly before the layer is fully dried out.
  • Another separate or supplementary procedure for improving the drying is to blow the drying air in a direct flow (with the air flowing from above the bed through the product) instead of the conventional reverse flow (from below the bed through the product). This measure reduces dusting and provides an improved quality product.
  • the flow rate (speed and/or time) of the drying air can also be used to control the drying of the layer.
  • the suitable time for applying the drying air depends on the apparatus used. When suitable parameters are once found, the apparatus can be adjusted to work accordingly.
  • drying phase After the drying phase the next cycle continues with a new spraying phase, rotating phase and drying phase.
  • conventional (lower) drying temperatures are preferably used and the air flow may be changed to reverse flow.
  • Coating cycles (usually about 60 cycles) are applied until a suitable coating is obtained.
  • the coated product is not finished and ready to be packed - it may still be an intermediate, as after the spraying and drying process the coating may not be totally crystallized.
  • the intermediate is therefore removed from the coating apparatus and fed to a storing tank. Tempering air is supplied to the tank in order to get the product tempered or conditioned. The final crystallization takes place in the conditioning tanks only, and there the crunchiness of the product is created.
  • the first type of syrup contains more gum and has a multiple role: 1) to seal the core and slow/prevent moisture migration between core and coating and vice versa 2) to prevent the coating from being friable (i.e. stick the coating to the pellet firmly, so that it will not flake off) 3) make the coating more flexible 4) form a good base for the main coating coats.
  • the first syrup (sealing) is typically used until an increase in pellet weight of typically about 10 to 30% has been achieved, then the coating syrup is used to build up the remainder of the coat.
  • this coating is designed to protect and act as a "key” for the further coats, it is important that the pellets are well coated with this material before progressing to the coating syrup, and this is conventionally done visually or by "feel” .
  • the syrups for a xylitol coating may, for instance, have a concentration of 72% (65% xylitol & 7% gum arabic) dry substance in the sealing syrup, and 74% (72% xylitol & 2% Gum Arabic) dry substance in the coating syrup.
  • the syrup preferably contains about 40 to 80 % xylitol on the total weight. It generally contains about 1-10 % or more, up to about 20 % of a gum such as Gum Arabic on the total weight.
  • the syrup may also contain other additives such as flavours, pigments, special sweeteners, active ingredients, etc.
  • the additives should be chosen so as not to adversely affect the crystallization process. Some insoluble additives may even accelerate the crystallization by providing crystal growth centers.
  • the syrup spraying temperature is generally maintained at 40 to 80 °C, typically about 50 °C.
  • the chosen temperature will depend on the concentration of the syrup and the drying conditions.
  • the present invention is suitable for providing hard coatings from solutions containing also other dissolved and/or suspended polyols, especially special sweeteners such as lactitol, maltitol, mannitol, isomalt, sorbitol, etc.
  • the direction of the air flow during the period of high temperature drying is preferably direct, while it is often preferred to use a reverse flow when drying at a conventional temperature in the initial period and/or at the end of the coating.
  • the direction of the flow of air may also be changed at other times during the coating procedure, for instance to alleviate dusting problems.
  • the temperature of the drying air may also be changed during the cycles themselves. Warm or hot air may be used in the beginning of the drying cycle and colder air during the end of the cycle, e.g. 1 to 2 minutes of warm/hot air and 1-2 minutes of cold/cool air.
  • Examples 1 to 3 were conducted on a batch size of 350 kg pellet centres, coated to a 50 % weight increase.
  • Examples 4 to 6 were conducted on a batch size 60 kg pellet centres, also coated to a 50 % weight increase.
  • the sealing syrup composition was xylitol 65 %, gum arabic 7 %, water 28 %; the coating syrup composition was xylitol 72 %, gum arabic 2 % , water 26 %.
  • the pellets On tasting the samples 2 weeks after production the pellets had a good gloss, with a smooth surface and little or no comer loss. The pellets had an acceptably crunchy coating.
  • the syrup appeared to be crystallizing rapidly giving rise to a rough surface. Due to the roughness a pause period had to be incorporated into the process. The degree of dusting in combination with the pause period caused a sticky period during the process. A number of multiples formed within the pan.
  • Direct air-flow was used in the process as opposed to the reverse air-flow utilized in the standard procedure. Direct air-flow reduces the effectiveness of the drying.
  • This batch followed an identical syrup dosage as applied during the standard batch. Changes were made during the processing whereby larger syrup applications could be made and drying times could be reduced significantly. Overall, this batch processed ⁇ 35% faster than the standard batch (188 minutes compared to 292 minutes for the standard). The batch also processed quicker than batch 1600/3.
  • the finished coating was very smooth and quite glossy. However, most of the pellets had well-rounded comers, a sign of abrasion during the process. The finished coating was crisp with a good crunch equal to the standard.
  • the product temperature was raised by 5°C, above that utilized for Trial 1200/4.
  • the drying air temperature for this trial was set at a maximum of 45 - 48 °C for much of the process.
  • Increasing the product temperature by 5 °C throughout this trial appeared to significantly reduce any problems associated with stickiness during the drying phases of the process, and to aid more rapid drying of the syrup coats.
  • the more efficient drying of the syrup applications allowed total drying times to be reduced, resulting in a faster process than Trial 1200/4 (177 minutes versus 213 minutes).
  • the quality of the finished pellet coating did not appear to be effected by the changes in the protocol.
  • the finished product had a slightly improved sheen over that observed for Trial 1200/4. Comer loss on the pellets was comparable between both batches. Crunchiness of the pellet coating was perhaps marginally superior to Trial 1200/4; otherwise there was little overall difference between the products.
  • the pellet crunch was not as crisp as that produced in trial 1200/4.
  • a batch of chewing gum pellet centres were coated to a 50 % weight increase with the same syrups as those used in Examples 1-6.
  • the initial layers were produced with an inlet air temperature of about 30 °C whereafter the inlet air temperature was raised to 40 °C for the actual coating.
  • the change in relative humidity (RH) of the outlet air was monitored at the increased temperature phase.
  • the relative humidity of the outlet air had a basic level of about 12 % measured as the RH of the air in the outlet tube during the pause, during which the bed was by-passed.
  • the RH of the outlet air was found to increase rapidly during the first 30 seconds of the drying, whereafter it decreased slowly as indicated in Table 2.
  • the drying sequence was between 2 and 3 minutes and the Table shows that some moisture that could have been dried off from the layer was intentionally left in the layer. By this control procedure the process could be speeded up considerably while ascertaining that the layer did not over-dry to a point where dusting would disturb the coating surface.
  • Two batches of chewing gum pellets (10 kg) were coated in a Driacoater 500/600 Vario equipment with a syrup containing 65% xylitol and 7% gum arabic in the sealing syrup and 72% xylitol and 2% gum arabic in the coating syrup.
  • the outlet air RH was monitored during the process.
  • the basic level for the RH of the outlet air was determined as the RH of the outlet air at the point at which the pellets were observed to be fully dried, and at which the RH of the air appeared to have reached a plateau.
  • the trigger point for the next syrup application was set at a point when the desired difference between the observed RH of the outlet air and the predetermined basic RH level was reached, i.e. a point 1-10% RH above the basic level RH of the outlet air. For example, if the basic level RH of the outlet air was 30%, and the desired difference in RH was 5%, then when the next syrup application would be applied when the measured RH of the outlet air reached 35%.
  • the temperature of the drying air was raised after the sealing phase from 30°C to 50°C.
  • the change to RH control was made during phase 4 onwards.
  • the RH of the outlet air was used to trigger syrup application when the RH was above its basic level.
  • Batch A set a target of applying the next syrup phase when the RH of the outlet air was -5% higher than the basic levels assessed in a previous trial with complete drying.
  • the batch progressed well with the addition of up to 5% RH to the basic level. During this batch the relative humidity of the inlet feed air was relatively high as the dew point in the air drier was monitored at -3°CTP. The batch was completed 32 minutes quicker than a standard trial.
  • Batch B intended to add 6 + % to the basic level RH of the outlet air.
  • the RH of the inlet air had changed to the dryer conditions of a dew point of -10°CTP.
  • the RH of the outlet air dropped very rapidly in this batch.
  • the coating time for the process was an improvement over the previous trial and coating times were reduced significantly compared to standard trials.

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EP01903845A 2000-02-03 2001-02-02 A process for hard panning of chewable cores and cores produced by the process Revoked EP1251745B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DK01903845T DK1251745T3 (da) 2000-02-03 2001-02-02 Fremgangsmåde til hård dragering af tygbare kerner og kerner frembragt ved fremgangsmåden

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI20000226 2000-02-03
FI20000226A FI117465B (fi) 2000-02-03 2000-02-03 Menetelmä pureskeltavien ytimien kovapinnoittamiseksi
PCT/FI2001/000098 WO2001056398A1 (en) 2000-02-03 2001-02-02 A process for hard panning of chewable cores and cores produced by the process

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EP1251745A1 EP1251745A1 (en) 2002-10-30
EP1251745B1 true EP1251745B1 (en) 2004-12-01

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EP01903845A Revoked EP1251745B1 (en) 2000-02-03 2001-02-02 A process for hard panning of chewable cores and cores produced by the process

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US (1) US6821535B2 (ko)
EP (1) EP1251745B1 (ko)
KR (1) KR100762728B1 (ko)
AT (1) ATE283641T1 (ko)
AU (1) AU2001231813A1 (ko)
DE (1) DE60107536T2 (ko)
ES (1) ES2232592T3 (ko)
FI (1) FI117465B (ko)
WO (1) WO2001056398A1 (ko)

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DE60107536D1 (de) 2005-01-05
FI20000226A (fi) 2001-08-04
FI117465B (fi) 2006-10-31
DE60107536T2 (de) 2005-12-15
FI20000226A0 (fi) 2000-02-03
ES2232592T3 (es) 2005-06-01
WO2001056398A1 (en) 2001-08-09
EP1251745A1 (en) 2002-10-30
AU2001231813A1 (en) 2001-08-14
KR20020076280A (ko) 2002-10-09
US20010018084A1 (en) 2001-08-30
ATE283641T1 (de) 2004-12-15
KR100762728B1 (ko) 2007-10-09

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